Chromable dyestuffs of the triarylmethane series and process of preparing them



Patented Sept. 15-, 1 942 CHROMABLE DYEsTUFFsoF THE, TRHRXLL METHANE SERIES AND rnoonss F PRE- PARING THEM Wilhelm Eckert and Karl Schilling, Frankfort- -on-the'-Main, Germany, assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware NoDraw-ing. Application Februar y ZO, 1940, Sei'ial No. 319,910. In Germany -=March-15;1 9?-9 13 Claims.

'Ihe present invention relates to chromable dyestuiispf the th-riarylmeth'ane series and to a process of preparing them. 7

In U. 'S. Patent 2,153,059 and in patent application Serial No. 259,286, filed March 1, 1939, there are described new dyestuffs of the triarylmethane series capable of being chromed and a process of preparing these dyestuffs by con-- densin'g one molecular proportion of the anhydride of hydroxybenzene-l.2;4.-tricarboxy1ic acid or ot 3-hydroxybenzene-l.2.4.-tricarboxyIic acid (5- or 3-hydroxytrirnelitic acid) or the eqiiivalent amountof the free acid with two molecular proportions of an N-s'ubstituted mami'ntiphenol. The same orisimilar dyestuffs are obtainable by coiidensingone molecularproportion ofan N-substituted m arninop'henol with a benzene-benzoicacid compound which is obtainable by condensation of one molecularproportion'of fi-hydroxybenzene-1.2.4-tricarboxylic acid or its anhydride or of 3-hydroxybenzene-L2A- tricarboxylic acid or its anhydride with only one molecular proportion of the N-substituted maminophenol.

We have found thatthe same or similar dyestufi's can successfully he produced by a process which comprises causing 3.6-diha1ogen-4'-hydroxy-5'carboxy-fiuoran or the isomeric 3.6- dihalogen-S-hydroxy-4'-carboXy-fiuoran of the formulae:

Hal O Hal i oo Hooo

Hal O\ Hal the corresponding compounds which derive'from 3-hydroxy-benzene 1.2.4-triizarboxylic acid and which have the formulae:

or a mixture rof these :isomeric compounds, :to react with ammonia or withan aliphatic, aromatic, 'hydroaromatic or heterocyclic" amino compound. The reaction is preferably I carried out by Inciting the ;reagents at a temperature of between: about 150 C. "and about 250 C., "favorablyyin thepresence (if Zinc chloride. The coinpounds "thus v obtained by replacing 'the .h'aldgeh atoms byfthe "amino'ra'dic'al may be -su1'fonated in order "to increase their 'water "solubility, if

necessary. p

suitahl amino compounds are monoand diall'zylamines and'ihydroxyalkylamines: H2'N-a1kyl,

HNCalkYD-a ffor' I'in's'tance monoand di' rnethyb,

40 monoand idieethyle, monosand di-propyL,

mono-andzdFbutyl-ammes, amino alkyl rsuif oni'c and alkyl taurinesgamino-tfatty acids, arylamines and arylamino -sulfonic and -carboxylic acids: HzN-aryl, HzN-aryl-SOaIiI, HzN-aryI-COOH, for instance aminobeniene, aininonaphthalene or a mixture of these isomeric compounds, or and substitution produc'tsthereof, hydroaromatic and heterocyclic amino compounds, for instance c and p-aminotetrahydronaphthalene, aminopyridine, amino-diphenylenoxide etc.

The said amino compounds may be substituted by radicals which are capable of being chromed. Thus, for instance, the various amino-salicylic acids may be used.

The replacement of the halogen atoms by simple amino groups may be performed by treating the said dihalogen fluosan compounds with ammonia or with a compound capable of splitting off ammonia or with an aryl sulfamide and subsequent saponification.

The new process is particularly advantageous as, in some cases, the dyestuffs are obtained with still better yields. Due to the extraordinarily wide variability as to the amino-compounds to be substituted for the halogen atoms, it is possible to produce many dyestuffs which otherwise could not or only diificultly be obtained in View of the fact that a great number of the correspondingly substituted m-aminophenols are only difiicultly accessible.

The dyestuffs thus obtained dye, for instance,

animal fibers from an acid bath very clear shades; by afterchroming the dyeings the fastness properties of the dyeings are essentially enhanced. The dyestufis are also suitable for the production of chromed prints on cotton and artificial silk. They may also be chromed in substance.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto; the parts are by weight:

l;. ,'86 parts of the compound which is obtainable by condensing one molecular proportion of -hydroxy-benzene-1.2.4-tricarboxylic acid with two molecular proportions of 1.3-dihydroxy-benzene and replacing the two hydroxy-groups in the 3- and 6-positions of the 3.6-dihydroxy-carbonhydroxy-fluoran thus obtained by chlorine atoms, which compound is the 3.6-dichloro-4'-hydroxy- 5-carboxy-fiuoran or of the isomeric 3.6-dichloro- 5-hydroxy-4'-carboxyfluoran or a mixture of these compounds, 207 parts of sodium l-methylamino-ethane-Z-sulfonate (sodium methyl taurine) of 62.9 per cent strength and 100 parts of anhydrous zinc chloride are melted together for 2 hours at 190 C. to 200 C. When cold, the finely pulverized melt is stirred with about 100 parts of hydrochloric acid of per cent strength, filtered with suction, washed with hydrochloric acid of 10 per cent strength and dried.

The dyestuff thus obtained is a red powder which dyes wool from an acid bath bright, bluish-red tints. By after-chroming these dyeings attain very good fastness properties. The dyestufi is also excellently suitable for the production of chromed printingsron cotton and artificial silk. The dyestuff has the following constitution:

or that of the isomeric compound:

CH3 CH3 or it is a mixture of these two isomeric compounds.

2. 86 parts of 3.6-dichloro-4-hydroxy-5-carboxy-fluoran or of the isomeric 3.6-di-chloro-5- hydroxyl'-carboxy-fluoran or of a mixture of these compounds are heated with 49 parts of 2.3-dimethyl-1-aminobenzene and 60 parts of anhydrous zinc chloride for 2 hours to 200 C. to 210 C. After cooling, the melt is finely pulverized and the powder obtained is boiled with about parts of hydrochloric acid of 20 per cent strength for removing the zinc chloride. The residue is filtered with suction, washed and treated with dilute sodium carbonate solution; the red solution formed is separated from the undissolved residue by filtration and the dyestuff obtained is precipitated from the filtrate by acidification. After drying, the dyestufi is a violet-red powder which is insoluble in water and is transformed by sulfonating it according to known methods into a watersoluble sulfonic acid which dyes wool from an acid bath bluishred tints. The fastness properties of these dyeings are considerably improved by after-chroming. The constitution of the dyestuff is illustrated by the following formulae:

CH3 CH3 CH3 or the dyestuff is a mixture of these isomeric compounds. It is also possible to prepare this dyestuff containing sulfo groups by condensing the dichloro-hydroxy-carboxy-fiuoran with 2.3- dimethyl-1-amino-benzenel-sulfonic acid.

3. 86 parts of 3.6-dichloro-4'-hydroxy-5'-carboxy-fluoran or the isomeric 3.6-dichloro-5-hydroxy-4'-carboxy-fiuoran or of a mixture of these compounds, 40 parts of aniline and60.

parts of anhydrous zinc chloride are heated for 1 hours to 200 C. to 21o C. After cooling the finely ground melt is boiled with hydrochloric acid of per cent strength for a prolonged time (about 1 hour). The residue is filtered with suction, Washed with water and treated with hot dilute sodium carbonate solution. The dyestuff solution is separated from the undissolved residue by filtration and the dyestuff is precipitated by acidifying it. It is insoluble in water and is transformed into a sulfonic acid by sulfonating it according to known methods. In this form it dyes wool from an acid bath reddish-violet tints. By after-chroming the shade is only slightly changed, but the fastness to wetting is essentially improved.

The dyestufi probably has the following composition:

coon

or it is a mixture of these isomeric compounds.

Instead of subsequently introducing the sulfo group it is also possible to use the l-amino-benzene--sulfonic acid as reaction component.

' 4. 86 parts of 3.6-dich1oro-4-hydroxy-5'-carboxy-fluoran or of the isomeric 3.6-dichloro-5'- hydroxy-'-carboxy-fiuoran or of a mixture of these compounds, 55 parts of l-aminol-methoxy-benzene and 60 parts of anhydrous zinc chloride are heated for 2 hours to 220 C. to 225 C. The melt is further treated as described in Example 3. After the sodium carbonate solution has been precipitated with dilute mineral acids and the precipitate has been dried the dyestuif is obtained in the form of a violet, water-insoluble powder which is transformed into watersoluble sulfonic acids by sulfonation. In this form it dyes wool bluish-violet tints. The shade becomes somewhat more red by after-chroming. The fastness to wetting is considerably enhanced. The constitution of the dyestuff is shown by the following formulae:

COO

or it is a mixture of these isomeric compounds.

5. 43 parts of 3.6-dich1oro-4-hydroXy-5-cai boxy-fiuoran or of the isomeric 3.6-dichloro5- hydroxy-l-carboxy-fluoran or of a mixture of these compounds, 60 parts of 8-amino-quinoline, 20 parts of anhydrous zinc chloride are melted together, while stirring, for 2 hours at 240 C;

After coo1ing,the melt is finely ground and boiled with about 500parts of hydrochloric acid of 3 The residue is filtered with suction, washed and dried; A blue powder is obtained which is insoluble in water and in dilute acids. By sulfonating the compound with ulfuric acid mono hydrate at room temperature it is converted into a water-soluble dyestuff which dyes wool from an acid bath blue'tints which become very fast by after-chroming. The dyestuff probably has the perature of between about 150 C. and about 250 following constitution: C. in the presence of zinc chloride.

NH O NH o a NazOS-U -SO;Na

OCH: C./ V OCH:

ooo'

HOOC/ H H 0 N 0 N o Na=0s-- \j-smm OCHa H 0 coo' or it is a mi u e of these isomeric compounds- 30 4. The process which comprises causing a com- We claim: pound of the formula: 1. The process which comprises causing a compound of the group consisting of 3.6-dihalogen- C1 4'-hydroxy-5'-carboxy fiuoran and the isomeric 3.6-diha1ogen-5'-hydroxy-4'-carboxy-fluoran and 3.6-diha10gen-3-hydroxy-4'-carboxy-fluoran and the isomeric 3.6-dihalogen-6'-hydroxy-5'-car- I boXy-fiuoran and mixtures of these isomeric compounds to react with a compound of the group 00 consisting of ammonia and. aliphatic, aromatic, H hydroaromatic and heterocyclic primary and secondary amino compounds.

2. The process which comprises causing a com- X pflund of group Conslstmg of h t' wherein one X represents the hydroxy group and g gfi l y- -5 gl zfi zf i g lsomerlg the other X the carboxylic acid group, to react 3-6:d;h:1g :fi:3 :hdrg: :ggi gi fig jgfi ai with an amino compound selected from the group the sl i 3 6 dihaligemfiuh g car consisting of primary and secondary amino compounds of the benzene series by melting the reboxyfiuoi an and mixtures of these isomeric comagents at a temperature of between about 0 pounds to react with a compound of the group o consisting of ammonia and aliphatic, aromatic, about 250 m the presence of mm ch10 hydroaromatic and heterocyclic primary and secondary amino compounds by melting the reagents at a temperature of between about 150 C. and about 250 C. in the presence of zinc chloride.

pound of the formula:

01 3. The process which comprises causing a com- O\ C1 pound of the formula;

o 01- Cl X wherein one X represents the hydroxy group X and the other X the carboxylic acid group, to

react with an unsulfonated amino compound sewherein one X represents the hydroxy group and 16011801 m the group consisting f p mary and the other X the carboxylic acid group, to react Secondary amino p u ds of the benzene $8- with a compound of the group consisting of ames by melting the e gen at a temperature of monia and aliphatic, aromatic, hydroaromatic between about C. and about 250 C. in the and heterocyclic primary and secondary amino p esence of zinc chloride and sulfonating the compounds by melting the reagents at a tem- 76 c mpound thus obtained.

5. The process which comprises causing a com-- 6. The process which comprises causing a compound of the formula:

X wherein one X represents the hydroxy group and the other X the carboxylic acid group, to react with aniline by melting a mixture of the reagents at about 200 C. to about 210 C. for about 1 /2 hours in the presence of anhydrous zinc chloride and sulfonating the compound thus obtained.

8. The process which comprises causing a compound of the formula:

wherein one X represents the hydroxy group and the other X the carboxylic acid group, to react with 1-amino-4-methoxy-benzene by melting a mixture of the reagents at about 220 C. to about 225 C. for about two hours in the presence of anhydrous zinc chloride and sulfonating the compound thus obtained.

9. The compounds of the formula:

wherein the His represent the same radical of the group consisting of aromatic, hydroaromatic and heterocyclic radicals and one Xstands for the hydroxy group and the other X for the carboxylic acid group.

10. The compounds of the formula:

wherein the Rs represent the same radical of the benzene series and one X represents the hydroxy group and the other X stands for the car- .boxylic acid group.

11. The compound of the formula:

CH3 CH1 H CH3 OH:

| I o i I NaOaS- rr-(I \UN some COO wherein one X represents the hydroxy group and the other X the carboxylic acid group, being a water-soluble dyestuff which dyes, for instance, wool from an acid bath bluish-red tints, the fastness properties of the dyeings being essentially enhanced :by atfter-chroming.

12. The compound of the formula:

H H O NM JTI brig-Sosa O l wherein one X represents the hydroxy group and the other X the zcarboxylic acid group, being a water-soluble dyestuff which dyes, for instance, wool from an acid bath reddish-violet tints, the fastness properties of the dyeings being essentially enhanced by after-chroming.

13. The compound of the formula:

wherein one X represents the hydroxy group and the other X the carboxylic acid group, being a water-soluble dyestuif which dyes, for instance, wool from an acid bath bluish-violet tints, the tfastness properties of the dyeings being essentially enhanced by after-chroming.

WILHELM ECKERT.

KARL SCHILLING.

OF CORREC-TI ON Patent No. 2,296,153; September 15, 19112.

WILLIAM ECKERT, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line L O, for the word "carbon" read carboxy-; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 15th day of April, A. D. 19%.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents. 

